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WO1997030028A2 - RECUPERATION DU ε-CAPROLACTAME - Google Patents

RECUPERATION DU ε-CAPROLACTAME Download PDF

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Publication number
WO1997030028A2
WO1997030028A2 PCT/NL1997/000033 NL9700033W WO9730028A2 WO 1997030028 A2 WO1997030028 A2 WO 1997030028A2 NL 9700033 W NL9700033 W NL 9700033W WO 9730028 A2 WO9730028 A2 WO 9730028A2
Authority
WO
WIPO (PCT)
Prior art keywords
caprolactam
process according
extraction
aqueous mixture
oligomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL1997/000033
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English (en)
Other versions
WO1997030028A3 (fr
Inventor
Rudolf Philuppus Maria Guit
Yvonne Helene Frentzen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke DSM NV
EIDP Inc
Original Assignee
DSM NV
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Priority claimed from MYPI96000650A external-priority patent/MY116498A/en
Priority claimed from EP96202436A external-priority patent/EP0826665A1/fr
Application filed by DSM NV, EI Du Pont de Nemours and Co filed Critical DSM NV
Priority to KR10-1998-0706368A priority Critical patent/KR100459817B1/ko
Priority to EP97902722A priority patent/EP0891327B2/fr
Priority to AU16739/97A priority patent/AU1673997A/en
Priority to CA002246459A priority patent/CA2246459A1/fr
Priority to DE69717976T priority patent/DE69717976T3/de
Priority to JP09529213A priority patent/JP2000512615A/ja
Priority to PCT/NL1997/000467 priority patent/WO1998017642A1/fr
Priority to KR10-1999-7003499A priority patent/KR100446372B1/ko
Priority to ES97935901T priority patent/ES2224262T3/es
Priority to EP97935901A priority patent/EP0958278B1/fr
Priority to CA002269292A priority patent/CA2269292A1/fr
Priority to JP10519249A priority patent/JP2001502688A/ja
Priority to DE69729119T priority patent/DE69729119T2/de
Priority to CN97180750A priority patent/CN1099412C/zh
Priority to AU38700/97A priority patent/AU3870097A/en
Priority to IDP972856A priority patent/ID18585A/id
Priority to MYPI97003767A priority patent/MY119509A/en
Priority to TW086101201A priority patent/TW496862B/zh
Publication of WO1997030028A2 publication Critical patent/WO1997030028A2/fr
Publication of WO1997030028A3 publication Critical patent/WO1997030028A3/fr
Priority to US09/134,756 priority patent/US6191274B1/en
Anticipated expiration legal-status Critical
Priority to US09/295,310 priority patent/US6207827B1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/16—Separation or purification

Definitions

  • the invention relates to a process to separate ⁇ -caprolactam from an aqueous mixture containing ⁇ -caprolactam and at least 0.5 wt% oligomers.
  • a process is known from US-A-5495016.
  • 6-aminocapronitrile is converted into crude ⁇ - caprolactam by reaction with water.
  • the resulting aqueous mixture comprises ammonia, ⁇ -caprolactam and oligomers.
  • By first separating ammonia by distillation an aqueous mixture is obtained comprising ⁇ -caprolactam and said oligomers.
  • ⁇ -caprolactam is separated from this mixture by distillation, in which the ⁇ -caprolactam and water is recovered as the top product and oligomers are recovered in a concentrated mixture as bottom product.
  • a disadvantage of this process is that at the high reboiler temperatures of the distillation column ⁇ -caprolactam will easily convert to more oligomers (2 wt.% absolute according to Example I of US-A-5495016) . Furthermore fouling of pipes and other process equipment because of solidification of the oligomers cannot be easily avoided.
  • the object of the invention is a process for the separation of ⁇ -caprolactam from aqueous mixtures comprising also oligomers in which the above mentioned disadvantages are avoided.
  • This object is achieved in that the separation is performed by extraction using an organic extraction agent.
  • Extraction is a known method of separating ⁇ - caprolactam from the reaction mixture obtained by the Beckmann rearrangement of cyclohexane oxime with sulfuric acid or oleum. After neutralization of the discharged rearrangement reaction mixture with ammonia, the ⁇ -caprolactam is separated from the ammonium sulfate by extraction with an organic solvent, such as benzene. No oligomers are formed in this process.
  • US-A-5495016 only mentiones distillation as separation method.
  • US-A-4730040 mentions the extraction of ⁇ - caprolactam from aqueous mixtures containing ⁇ - caprolactam using chloroform. This patent is however silent if ⁇ -caprolactam can also be separated from aqueous mixtures also containing oligomers.
  • US-A-3485821 describes a process for the preparation of ⁇ -caprolactam by heating an aqueous mixture of 6-aminocaproic acid. In the examples ⁇ - caprolactam is isolated by extraction with chloroform. Only in Example 13 of this patent publication some polyamide is also present in the aqueous ⁇ -caprolactam containing mixture. No extraction is performed in this example to isolate ⁇ -caprolactam. The polyamide was separated from the aqueous mixture by cooling and filtration.
  • US-A-4013640 describes the extraction of water soluble amides, such as ⁇ -caprolactam, n- butyramide and n-valeramide, from an aqueous mixture using alkyl phenol solvents as the extraction agent.
  • This patent publication mentions a wide range of linear and cyclic amides which can be extracted. It was therefore not to be expected that ⁇ -caprolactam could be successivefully separated from other amides such as oligomers.
  • the oligomers are generally oligomers (dimers and trimers mostly) of 6-aminocaproic acid or of 6- aminocaproamide.
  • concentration oligomers in the aqueous mixture is higher than 0.5 wt.%.
  • the invention relates especially to the separation of ⁇ -caprolactam from aqueous mixtures obtained in (a) a process to prepare ⁇ -caprolactam in which 6-aminocapronitrile is converted into crude ⁇ - caprolactam by reaction with water as described in for example US-A-5495016, (b) a process to prepare ⁇ - caprolactam by cyclization of 6-aminocaproic acid in water as described in for example US-A-4730040 or (c) in a comparable process as under (b) in which the starting mixture comprises 6-aminocaproic acid and 6- aminocaproamide.
  • the aqueous mixture obtained in processes (a) and (c) will also contain ammonia which is a side- product of the reaction to ⁇ -caprolactam starting from 6-aminocapronitrile or 6-aminocaproamide. It is advantageous to separate the ammonia prior to the extraction, for example by distillation or steam stripping. In the distillation any unconverted 6- aminocapronitrile (in process (a)) and part of the water will generally be separated as well.
  • the concentration of the ⁇ -caprolactam, optionally 6- aminocaproic acid, optionally 6-aminocaproamide and oligomers in the aqueous mixture obtained after such an ammonia separation will be preferably higher than 10 wt%.
  • the conditions of such process are preferably as described below.
  • the concentration of ammonia and ammonia equivalents is below 5 wt.%.
  • ammonia equivalents is meant that every mol of a compound having a -C(0)-NH 2 group is calculated as a mol NH 3 .
  • the total molar amount of NH 3 thus calculated can be expressed in a weight % of NH 3 . This number should be below 5 wt.% and preferably below 3 wt.%.
  • the concentration of ⁇ -caprolactam, 6- aminocaproic acid, 6-aminocaproamide and oligomers is preferably between 5-50 wt.% and more preferably between 10-35 wt.%.
  • the concentration of ⁇ -caprolactam is preferably between 5-30 wt.%.
  • the temperature is preferably between 270 and 350°C, more preferably higher than 290°C.
  • the pressure is preferably between 5.0 and 20 MPa. Normally the pressure will be greater than or equal to the resulting pressure of the liquid reaction mixture and the temperature employed.
  • the reaction to ⁇ -caprolactam can be performed continuously.
  • the aqueous mixture obtained in the extraction according to the invention is preferably recycled to the cyclization processes as (a)-(c) here described. It has been found that the compounds, for example 6-aminocaproic acid, 6-aminocaproamide and oligomers which are present in this mixture can react to ⁇ -caprolactam in a high yield. Thus by using extraction to isolate ⁇ -caprolactam a valuable recycle stream is also obtained which can be successivefully used to prepare more ⁇ -caprolactam.
  • the aqueous phase obtained in the extraction will contain oligomers and optionally 6-aminocaproamide and/or 6-aminocaproic acid.
  • the extraction agent is preferably an organic solvent which is substantially immiscible with water.
  • substantially immiscible is here meant that the mixture of organic solvent and the aqueous mixture results in two segregated phases at the extraction temperature.
  • the mutual solubility under the conditions of the extraction is not higher than 30 wt.% and more preferably less than 20 wt.% .
  • Possible extraction agents are aromatic solvents, for example benzene, toluene, xylene; ethers, for example diethylether, methyl tert-buthylether;
  • chlorinated hydrocarbons with 1 to 10 carbon atoms are used. Examples are chloroform, dichloromethane and 1,1,1-trichloroethane.
  • Another class of preferred extraction agents are phenol and even more preferred are alkyl phenols.
  • a preferred class of alkyl phenols have a boiling point which is higher than that of ⁇ -caprolactam. It has been found that ⁇ -caprolactam can be separated from especially oligomers, using this class of extraction agents.
  • the extraction agent can preferably be an alkyl phenol having a boiling point higher than the boiling point of ⁇ -caprolactam, which is 270°C at 1 bar.
  • Alkyl phenols have a high boiling point at atmospheric pressure. Therefore, boiling points are advantageously compared at reduced pressures of, for example, 1.3 kPa (10 mmHg).
  • Caprolactam has a boiling point of 140°C at 10 mmHg, while dodecyl phenol, for example, has a boiling point of 190°C at that pressure.
  • the boiling point of the alkyl phenol is more than about 5°C, and in particular, more than about 15°C higher than the caprolactam boiling point at 1.3 kPa (10 mmHg).
  • the upper limit to the normal boiling point of the alkyl phenol is about 400°C.
  • the alkyl phenol preferably is non-azeotropic with ⁇ -caprolactam. Mixtures of alkyl phenols can also be used.
  • An alkyl phenol is phenol substituted with one or more alkyl groups.
  • the total number of carbon atoms of the alkyl group(s) is preferably between 6-25 and more preferably between 9-15.
  • specific alkyl phenolic compounds include dodecyl phenol, octyl phenol, nonyl phenol, n-hexyl phenol, 2,4-diisobutyl phenol, 2-methyl-4,6-di-tert-butyl phenol, 3-ethyl-4,6- di-tert-butyl phenol, 2,4,6-tri-tert-butyl phenol, and mixtures of any thereof.
  • U.S. Patent No. 4013640 discloses additional alkyl phenols, the complete disclosure of which is hereby incorporated by reference.
  • More preferred extracion agents are (cyclic) aliphatic organic compounds having one or more hydroxy groups which are liquid under the extraction conditions and substantially immiscible with water.
  • Such (poly)alcohols have preferably 5-12 carbon atoms.
  • These extraction agents are preferred because they have a better extraction efficiency than the chloronated organic compounds and are more inert than most of the phenol like compounds as described above.
  • These extraction agents are furthermore preferred because their use does not result in any environmetnal objections.
  • Examples of compounds having two hydroxy groups are hexanediol, nonanediol, neopentylglycol, methyl-methylpropanediol, ethyl-methylpropanediol or butyl-methylpropanediol.
  • Examples of compounds having one hydroxy group are cyclohexanol, 4-methyl-2-pentanol, 2-ethyl-l-hexanol, 2-propyl-l-heptanol, n-octanol, iso-nonylalcohol, n- decylalcohol and mixtures of linear and branched C 8 - alcohols, mixtures of linear and branched C 9 -alcohols and mixtures of linear and branched C 10 -alcohols. Mixtures of the above mentioned alcohols can also be used.
  • a back wash can be performed by extracting the alcohol phase containing the ⁇ - caprolactam with water. This can be performed in a continuously operated process by adding water to the top of an extraction column while the aqueous mixture is fed at a lower point of the column. The back wash can also be performed in a seperate column.
  • the amount of organic extraction agent is not particularly limited provided that the advantages of the present invention can be achieved.
  • the upper limit, for example, is not believed critical but depends on process economy.
  • the extraction step is carried out at a temperature which is higher than the melting point of the organic extraction agent.
  • the temperature of extraction can be generally between room temperature and 200°C and preferably between 20 and 170°C.
  • the pressure during the extraction step is not generally critical and can be, for example, between about 0.1 MPa and about 2.0 MPa, and preferably, between about 0.1 MPa and about 0.5 MPa.
  • the extraction can be carried out in well known extraction apparatus, for example a counter current column, a series of mixer settlers, rotating disc contactors or pulsed packed columns.
  • the extraction step yields a ⁇ -caprolactam- containing organic phase which, in general, contains up to 50 wt.% ⁇ -caprolactam.
  • ⁇ -caprolactam may be recovered from the organic extraction agent by known separation methods, for example distillation and extraction. Preferably distillation is used. Especially when a higher boiling extraction agent is used as described above.
  • the organic phase is preferably reused in the extraction according to the invention.
  • a purge or a separate purification may be performed.
  • the liquid ⁇ -caprolactam obtained in the distillation may be subsequently further purified as for example exemplified in US-A-5496941.
  • the purification of the extracted and distilled ⁇ -caprolactam comprises the following steps: 1) contacting ⁇ -caprolactam at from 30 to 80°C and from 0.1 to 0.5 MPa over an ion exchanger containing terminal acid groups,
  • step (2) treating the mixture obtained in step (1) with hydrogen at from 50° to 150°C and from 0.15-25 MPa in the presence of a hydrogenation catalyst and
  • Steps (1) and (2) can be optionally performed in water or another solvent, for example the extraction agent as described above.
  • This purification procedure results in ⁇ -caprolactam of very good quality.
  • the ion exchange and hydrogenation treatment are known methods for purifying ⁇ -caprolactam obtained by Beckmann rearrangement and can be performed by these well known methods .
  • the purification of the distilled ⁇ -caprolactam is achieved by crystallization in a process of concentrating.
  • the crystallized ⁇ -caprolactam resulting from concentrating is generally sufficiently pure to be used directly.
  • the mother liquor can be purified, for example by means of distillation.
  • composition of the resulting mixtures of the experiments are sometimes expressed in mol percentages.
  • the molar percentage of a component is represented by the molar fraction (* 100%) which can theoretically convert to ⁇ -caprolactam.
  • 50 mol 6-aminocaproic acid and 25 mol dimers can contribute to 100 mol. ⁇ -caprolactam.
  • the molar contribution will be 50 mol% 6-aminocaproic acid and 50 mol% dimers (totaling 100 mol%).
  • Example I 200 ml of a mixture of 20 wt.% ⁇ -caprolactam
  • 0.6 wt.% oligomers and 5 wt.% 6-aminocaproic acid in water was mixed well, long enough to reach equilibrium, with 200 ml chloroform at room temperature and 0.1 MPa.
  • the water phase was separated from the chloroform by phase separation.
  • the water phase was again mixed with 200 ml chloroform as above and separated from the chloroform by phase separation.
  • the two chloroform phases were combined and analyzed by high pressure liquid chromatography (HPLC).
  • HPLC high pressure liquid chromatography
  • the water phase was also analyzed and the partition coefficient of ⁇ -caprolactam was 0.74.
  • the partition coefficient is defined as the concentration in the organic extraction agent divided by the concentration in the aqueous phase at (almost) equilibirum conditions. No detectable amount of 6- aminocaproic acid or oligomers ( ⁇ 0.01 wt.%) was found in the chloroform phase.
  • Example I was repeated with dichloromethane.
  • the partition coefficient was 0.84. No detectable amount of 6-aminocaproic acid or oligomers ( ⁇ 0.01 wt.%) was found in the dichloromethane phase.
  • Example I was repeated with methyl tert- butylether.
  • the partition coefficient was 0.1. No detectable amount of 6-aminocaproic acid or oligomers ( ⁇ 0.01 wt.%) was found in the tert-butylether phase.
  • An aqueous mixture containing 15 wt.% 6- aminocaproic acid and 1 wt.% ammonia was continuosly fed at a rate of 630 g/hr to a plugflow reactor (almost no backmixing) at a constant temperature of 300°C (maintained with the use of an oil bath) , a pressure of 10 MPa and at a residence time of 30 minutes.
  • the molar yield to ⁇ -caprolactam was 81 mol%. 12 mol% oligomers and 7 mol% of 6-aminocaproic acid and 6-aminocaproamide was present. 200 ml of this mixture was subjected to an extraction as described in Example I.
  • the partition coefficient for ⁇ -caprolactam was as in Example I. No detectable amounts ( ⁇ 0.01 wt.%) of 6-aminocaproic acid, 6-aminocaproamide or oligomers were found in the chloroform phase.
  • Example I was repeated using the aqueous mixture obtained in Example 1 of US-A-5495016 named "mixture 1" containing 90 wt.% water, 7,6 wt.% ⁇ - caprolactam and 2,4 wt.% high boilers (oligomers).
  • the partition coefficient for ⁇ -caprolactam was as in Example I and no detectable amount of high boilers (oligomers) or 6-aminocaproic acid was found in the chloroform phase.
  • Example V was repeated at 80°C using the same volume of dodecylphenol.
  • the partition coefficient of ⁇ -caprolactam was about 11. No detectable amount of oligomer was present in the organic phase.
  • Examples I-VI illustrate that ⁇ -caprolactam can be successivefully separated from aqueous mixtures containing 6-aminocaproic acid, 6-aminocaproamide and oligomers. These batch examples also show that an almost 100% separation of ⁇ -caprolactam is possible in a continuously operated extraction; for example in a counter current extraction column or in a series of mixer/settiers.
  • a mixture having a composition of 21.5 mol% 6-aminocaproic acid (6ACA), 45.9 mol% 6-aminocaproamide (6ACAM), 27.5 mol% ⁇ -caprolactam (CAP), 2.1 mol% methyl 6-aminocaproate (M6AC) and 3.0 mol% oligomers with a total concentration of 12.4 wt.% of these compounds in water was continuously fed at a rate of 571 g/hr together with a recycle stream (see below) to the top of a steamstripper column (operated at 0.1 MPa). Steam was generated in a reboiler of the column and no additional water was added.
  • the liquid bottom stream which left the steamstripper did not contain any detectable amounts of methanol and ammonia.
  • This aqueous stream consisted of 12.7 wt.% of 6ACA, 6ACAM, M6AC, CAP and oligomers.
  • This aqueous mixture was subsequently continuously fed to a cyclization reactor, a plugflow reactor (almost no backmixing), at a constant temperature of 320°C (maintained with the use of an oil bath) , a pressure of 12 MPa and at a residence time of 30 minutes.
  • a cyclization reactor a plugflow reactor (almost no backmixing)
  • a constant temperature of 320°C maintained with the use of an oil bath
  • a pressure of 12 MPa at a residence time of 30 minutes.
  • the liquid aqueous stream contained 15.1 wt.% products of which 89 mol% ⁇ - caprolactam, 8 mol% oligomers and 3 mol% of 6ACA(M).
  • This aqueous mixture was subsequently fed (480 g/hr) to the bottom of a continuously operated counter current extraction column.
  • the partition coefficient of ⁇ -caprolactam was about 1.65 (The water phase contained 4.28 wt.% ⁇ - caprolactam and the alkanol phase contained 7.06 wt.% ⁇ -caprolactam). No detectable amounts of 6ACA, 6ACAM or oligomers).
  • the alcohol phase contained 7 wt.% water.
  • Example VIII was repeated using the same volume of 2-ethyl-l-hexanol as the extraction agent.
  • the partition coefficient of ⁇ -caprolactam was 1.16 (the water phase contained 5.23 wt.% ⁇ -caprolactam and the alkanol phase contained 6.09 wt.% of 6ACA, 6ACAM and oligomers were found in the alcohol phase.
  • the alcohol phase contained 2.9 wt.% water.
  • Example VIII was repeated using an aqueous mixture containing 15.5 wt.% ⁇ -caprolactam, 5.2 wt.% 6- aminocaproic acid, 17.4 wt.% 6-aminocaproamide and 5.6 wt.% oligomers at 80°C.
  • the partition coefficient of ⁇ -caprolactam was 3.3. No detectable amounts of 6-aminocaproic acid and oligomers of 6-aminocaproic acid were found in the alcohol phase.
  • the partition coefficient of 6- aminocapr ⁇ amide and oligomer of 6-aminocaproamide was

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Polyamides (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour séparer le epsilon -caprolactame d'un mélange aqueux contenant du epsilon -caprolactame et au moins 0,5 % en poids d'oligomères. La séparation se fait par extraction, au moyen d'un agent d'extraction organique. Le mélange aqueux peut être obtenu par un procédé de préparation du epsilon -caprolactame à partir du 6-aminocapronitrile ou par un procédé de préparation du epsilon -caprolactame à partir de l'acide 6-aminocaproïque.
PCT/NL1997/000033 1996-02-17 1997-02-05 RECUPERATION DU ε-CAPROLACTAME Ceased WO1997030028A2 (fr)

Priority Applications (20)

Application Number Priority Date Filing Date Title
KR10-1998-0706368A KR100459817B1 (ko) 1996-02-17 1997-02-05 수성혼합물로부터ε-카프로락탐의분리방법
EP97902722A EP0891327B2 (fr) 1996-02-17 1997-02-05 Recuperation du epsilon-caprolactame de melanges aqueux
AU16739/97A AU1673997A (en) 1996-02-17 1997-02-05 Recovery of Caprolactam
CA002246459A CA2246459A1 (fr) 1996-02-17 1997-02-05 Recuperation du .epsilon.-caprolactame
DE69717976T DE69717976T3 (de) 1996-02-17 1997-02-05 Gewinnung von epsilon-caprolactam aus wässrigen gemischen
JP09529213A JP2000512615A (ja) 1996-02-17 1997-02-05 ε―カプロラクタムの回収
DE69729119T DE69729119T2 (de) 1996-10-21 1997-08-14 VERFAHREN ZUM ABTRENNEN VON ε-CAPROLACTAM VON 6-AMINOCAPRONAMID UND 6-AMINOCAPRONAMIDOLIGOMEREN
CN97180750A CN1099412C (zh) 1996-10-21 1997-08-14 从6－氨基己酰胺和6－氨基己酰胺低聚物分离ε－己内酰胺的方法
KR10-1999-7003499A KR100446372B1 (ko) 1996-10-21 1997-08-14 6-아미노카프로아미드와 6-아미노카프로아미드 올리고머에서 ε-카프로락탐의 분리방법
CA002269292A CA2269292A1 (fr) 1996-10-21 1997-08-14 Procede pour separer de l'epsilon-caprolactame contenu dans du 6-aminocaproamide et des oligomeres de 6-aminocaproamide
AU38700/97A AU3870097A (en) 1996-10-21 1997-08-14 Process to separate epsilon-caprolactam from 6-aminocaproamide and 6-aminocaproamide oligomers
ES97935901T ES2224262T3 (es) 1996-10-21 1997-08-14 Procedimiento para separar epsilon-caprolactama de 6-aminocaproamida y oligomeros de 6-aminocaproamida.
EP97935901A EP0958278B1 (fr) 1996-10-21 1997-08-14 Procede pour separer de l'epsilon-caprolactame contenu dans du 6-aminocaproamide et des oligomeres de 6-aminocaproamide
PCT/NL1997/000467 WO1998017642A1 (fr) 1996-10-21 1997-08-14 Procede pour separer de l'epsilon-caprolactame contenu dans du 6-aminocaproamide et des oligomeres de 6-aminocaproamide
JP10519249A JP2001502688A (ja) 1996-10-21 1997-08-14 ６―アミノカプロアミド及び６―アミノカプロアミドオリゴマーからε―カプロラクタムを分離するための方法
IDP972856A ID18585A (id) 1996-10-21 1997-08-15 Proses untuk memisahkan epsilon-kaprolaktam dari 6-aminokaproamida dan oligomer 6-aminikaproamida
TW086101201A TW496862B (en) 1997-02-05 1997-08-16 Recovery of epsi-caprolactam
MYPI97003767A MY119509A (en) 1996-10-21 1997-08-16 Process to separate (permittivy)-caprolactam from 6-aminocaproamide and 6- aminocaproamide oligomers
US09/134,756 US6191274B1 (en) 1996-02-17 1998-08-17 Recovery of ε-caprolactam
US09/295,310 US6207827B1 (en) 1996-10-21 1999-04-21 Process to separate ε-caprolactam from 6-aminocaproamide and 6-aminocaproamide oligomers

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
MYPI96000650A MY116498A (en) 1995-03-01 1996-02-17 Process for the preparation of é - caprolactam
MYPI9600650 1996-02-17
EP96202436.0 1996-09-02
EP96202436A EP0826665A1 (fr) 1996-09-02 1996-09-02 Récupération d'epsilon-caprolactam de mélanges aquex
EP96202931 1996-10-21
EP96202931.0 1996-10-21

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1997/000467 Continuation-In-Part WO1998017642A1 (fr) 1996-10-21 1997-08-14 Procede pour separer de l'epsilon-caprolactame contenu dans du 6-aminocaproamide et des oligomeres de 6-aminocaproamide

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US09/134,756 Continuation US6191274B1 (en) 1996-02-17 1998-08-17 Recovery of ε-caprolactam
US09/295,310 Continuation US6207827B1 (en) 1996-10-21 1999-04-21 Process to separate ε-caprolactam from 6-aminocaproamide and 6-aminocaproamide oligomers

Publications (2)

Publication Number Publication Date
WO1997030028A2 true WO1997030028A2 (fr) 1997-08-21
WO1997030028A3 WO1997030028A3 (fr) 1997-09-25

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Application Number Title Priority Date Filing Date
PCT/NL1997/000033 Ceased WO1997030028A2 (fr) 1996-02-17 1997-02-05 RECUPERATION DU ε-CAPROLACTAME

Country Status (12)

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US (1) US6191274B1 (fr)
EP (1) EP0891327B2 (fr)
JP (1) JP2000512615A (fr)
KR (1) KR100459817B1 (fr)
CN (1) CN1085978C (fr)
AU (1) AU1673997A (fr)
CA (1) CA2246459A1 (fr)
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WO1998041502A1 (fr) * 1997-03-17 1998-09-24 Dsm N.V. Procede de purification de caprolactame
EP1280768B1 (fr) * 2000-05-03 2009-12-09 Basf Se Procede de preparation de caprolactame a partir de 6-aminocapronitrile

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CN111122720B (zh) * 2019-12-11 2022-09-02 湖北三宁碳磷基新材料产业技术研究院有限公司 己内酰胺、6-氨基己酰胺和6-氨基己腈的分析方法
CN118751176B (zh) * 2024-08-29 2025-01-14 南京大学 以环己酮肟液相重排产物制氨基己腈的节能装置和方法

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WO1998017642A1 (fr) * 1996-10-21 1998-04-30 Dsm N.V. Procede pour separer de l'epsilon-caprolactame contenu dans du 6-aminocaproamide et des oligomeres de 6-aminocaproamide
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EP1280768B1 (fr) * 2000-05-03 2009-12-09 Basf Se Procede de preparation de caprolactame a partir de 6-aminocapronitrile

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WO1997030028A3 (fr) 1997-09-25
AU1673997A (en) 1997-09-02
TW420662B (en) 2001-02-01
CA2246459A1 (fr) 1997-08-21
EP0891327A2 (fr) 1999-01-20
DE69717976D1 (de) 2003-01-30
EP0891327B2 (fr) 2007-06-27
JP2000512615A (ja) 2000-09-26
US6191274B1 (en) 2001-02-20
CN1085978C (zh) 2002-06-05
ID16013A (id) 1997-08-28
CN1217712A (zh) 1999-05-26
DE69717976T2 (de) 2003-11-06
EP0891327B1 (fr) 2002-12-18
DE69717976T3 (de) 2008-09-18
KR100459817B1 (ko) 2005-05-16
KR19990082629A (ko) 1999-11-25
ES2188891T3 (es) 2003-07-01

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